CN109675599B - Nitrogen-doped carbon-coated molybdenum carbide and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated molybdenum carbide and preparation method and application thereof Download PDFInfo
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- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 77
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
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- 238000004090 dissolution Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
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- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 7
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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- B01J35/396—
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- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of nano material preparation, and discloses nitrogen-doped carbon-coated molybdenum carbide and a preparation method and application thereof. According to the invention, diammonium hydrogen citrate is used as a complexing agent and a carbon source, soluble molybdenum salt is used as a molybdenum source, hydrazine hydrochloride is used as an auxiliary coordination agent, molybdenum/diammonium hydrogen citrate gel is firstly prepared by a sol-gel method, and then nitrogen-doped carbon-coated nano molybdenum carbide is obtained by high-temperature carbonization and reduction in an argon atmosphere. According to the invention, the molybdenum element and the carbon element can be mixed at an atomic level by a sol-gel method, so that the agglomeration growth of molybdenum carbide nanoparticles during a high-temperature reduction reaction is inhibited, and the nitrogen-doped carbon-coated nano molybdenum carbide electrocatalytic material with uniform structure and distribution is obtained, and has excellent hydrogen production performance by electrocatalytic decomposition of water.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to nitrogen-doped carbon-coated molybdenum carbide and a preparation method and application thereof.
Background
The large-scale production of hydrogen by the electrochemical method has the advantages of low energy consumption, high purity, environmental friendliness and the like, so that the method has wide application prospect. Currently, the noble metal platinum (Pt) is the best electrocatalytic Hydrogen Evolution (HER) catalyst, but its high cost and instability in an electrolytic hydrogen production plant remain major challenges for the use of Pt catalysts. Therefore, the development of electrocatalysts replacing Pt is still at the front of technical research, and in recent years, researchers at home and abroad have conducted a great deal of research on electrocatalysts composed of transition metal groups (Ni, Fe, Co, W, Mo, etc.). In order to reduce the overpotential of HER, researchers have searched for various materials composed of transition metals, such as transition metal carbides, transition metal sulfides, transition metal nitrides, and transition metal phosphides. Although a significant reduction in catalytic overpotential has been achieved, there is still the potential to push this threshold further down to close to the Pt electrocatalyst.
Among the numerous transition metal carbides, molybdenum element carbides have better HER properties. Density Functional Theory (DFT) calculations for molybdenum carbide indicate that the hybridization of the d-orbital of metallic molybdenum with the s-and p-orbitals of carbon causes the d-band structure of molybdenum carbide to broaden, resulting in the formation of a d-band structure similar to Pt, which makes it one of the most promising alternatives to expensive Pt group catalysts. Research has shown that reducing the particle size of molybdenum carbide and doping of hetero atoms can improve the hydrogen evolution performance of the material (ACS Catalysis,2014,4, 2658-. Meanwhile, it can be speculated from the relationship between the material structure and the hydrogen evolution activity that the porous nano material with a large number of exposed defect sites on the surface has better hydrogen evolution activity than a zero-dimensional or one-dimensional material with the same composition, but the hydrogen evolution activity of the molybdenum carbide material in the existing research is still a gap compared with that of a platinum-based catalyst, the initial potential is about 70-90mV lower than that of a Pt/C catalyst, and further intensive research is needed to improve the catalytic performance.
Carbon materials have the potential to act as highly efficient stable HER catalysts due to their resistance to acids and bases, high conductivity, etc., but have weak hydrogen adsorption capacity (Gibbs free energy of Hydrogen Δ G)H-1.3 eV; while excellent HER catalysts tend to have Δ G of 0eVHValue) that generally exhibit very slow catalytic kinetics. Although B, N, S, P element doping can improve the hydrogen adsorption capacity of the carbon material, the carbon-based catalyst doped with the non-metal elements still has larger delta GHValue (b)>0.5eV) and poor HER activity (adv. funct. mater.2018,1706523) whereas carbon-coated metal/alloy-type catalysts (catalytically active sites are considered on a superficial carbon layer, called "armor" catalysts due to their excellent catalytic activity and stability) have received much attention in recent years, their overpotential η10Can be reduced to 100 mV. Therefore, the development of carbon composite catalysts is of great interest for the development of HER catalysts with platinum-like properties. At present, the preparation of carbon-coated nano molybdenum carbide electrocatalysts remains a great challenge.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a preparation method of nitrogen-doped carbon-coated molybdenum carbide, which comprises the steps of firstly preparing molybdenum/diammonium hydrogen citrate gel by a sol-gel method by using diammonium hydrogen citrate as a complexing agent and a carbon source, soluble molybdenum salt as a molybdenum source and hydrazine hydrochloride as an auxiliary coordination agent, and then carrying out high-temperature carbonization and reduction in an inert atmosphere or a reducing atmosphere to obtain the nitrogen-doped carbon-coated nano molybdenum carbide.
The invention also aims to provide the nitrogen-doped carbon-coated molybdenum carbide prepared by the method;
the invention further aims to provide application of the nitrogen-doped carbon-coated molybdenum carbide.
The purpose of the invention is realized by the following scheme:
a preparation method of nitrogen-doped carbon-coated molybdenum carbide comprises the following steps:
(1) preparing a gel: dissolving soluble molybdenum salt in water, adding diammonium hydrogen citrate, adding hydrazine hydrochloride after complete dissolution, uniformly mixing, adjusting the pH value of the solution to 5.5-7 by using ammonia water, heating and reacting for a period of time, continuously heating and stirring until the solution is evaporated to dryness to obtain gel, and further heating and dehydrating the obtained gel to obtain dry gel;
(2) preparing nitrogen-doped carbon-coated nano molybdenum carbide: and (2) uniformly grinding the dried gel obtained in the step (1), putting the dried gel into a tubular furnace for high-temperature carbonization and reduction, introducing inert gas or reducing gas in the reaction process, and obtaining the target product nitrogen-doped carbon-coated nano molybdenum carbide after the reaction is finished.
The soluble molybdenum salt in the step (1) includes but is not limited to ammonium molybdate, molybdenum chloride, sodium molybdate and the like.
The dosage of the soluble molybdenum salt, the diammonium hydrogen citrate and the hydrazine hydrochloride in the step (1) meets the following requirements: the mass ratio of diammonium hydrogen citrate to soluble molybdenum salt is (0.5-10) to 1; the mass ratio of the hydrazine hydrochloride to the soluble molybdenum salt is (0.1-2) to 1;
preferably, the soluble molybdenum salt, diammonium hydrogen citrate and hydrazine hydrochloride in the step (1) are used in the following amounts: the mass ratio of diammonium hydrogen citrate to soluble molybdenum salt is (1-3) to 1; the mass ratio of the hydrazine hydrochloride to the soluble molybdenum salt is (0.3-0.44): 1;
the water in the step (1) is only used as a reaction medium, so that the dosage of the water only needs to be enough to completely dissolve the added soluble molybdenum salt, diammonium hydrogen citrate and hydrazine hydrochloride.
The heating reaction in the step (1) for a period of time is carried out by heating to 30-50 ℃ and reacting for 4-8 h;
heating and stirring in the step (1) until the gel is evaporated to dryness, namely heating to 60-80 ℃ and stirring for 4-24 hours to evaporate to dryness to obtain the gel; the step of further heating for dehydration refers to heating to 100-200 ℃ for reaction for 4-24 h to further dehydrate the gel to obtain dry gel;
the high-temperature carbonization reduction in the step (2) is to react for 2-12 hours at 600-1200 ℃;
the inert atmosphere or reducing gas in step (2) includes, but is not limited to, nitrogen, argon, hydrogen, and argon/hydrogen mixture.
The nitrogen-doped carbon-coated nano molybdenum carbide prepared by the method.
The nitrogen-doped carbon-coated nano molybdenum carbide prepared by the method is applied as an electrocatalytic material, in particular to the application of the electrocatalytic material in preparing hydrogen by catalyzing and decomposing water.
The mechanism of the invention is as follows:
the method comprises the steps of firstly dissolving soluble molybdenum salt in water, then adding diammonium hydrogen citrate, wherein the diammonium hydrogen citrate cannot be in complex coordination with molybdenum salt ions, and adding hydrazine hydrochloride can promote the complex coordination of the diammonium hydrogen citrate and the molybdenum salt ions; and adjusting the pH value of the solution to be between 5.5 and 7.0 by using ammonia water, and placing the solution at the temperature of between 30 and 50 ℃ for reaction to further promote complexation coordination of diammonium hydrogen citrate and molybdenum salt ions. After reacting for a period of time at 30-50 ℃, complexing and coordinating diammonium hydrogen citrate and molybdenum salt ions completely, stirring at 60-80 ℃ and evaporating water to obtain gel, further dehydrating the gel at 100-200 ℃ to obtain dry gel, reacting the dry gel at 600-1200 ℃ in an inert gas or reducing gas atmosphere, carbonizing diammonium hydrogen citrate to obtain nitrogen-doped carbon in a high-temperature calcination process, and reducing substances such as carbon monoxide, carbon dioxide, methane, carbon and the like generated in the diammonium hydrogen citrate carbonization process can reduce and carbonize molybdenum to obtain nano molybdenum carbide. Therefore, the target product of the nitrogen-doped carbon-coated nano molybdenum carbide is obtained after the reaction is finished. Compared with a bulk molybdenum carbide material, the nitrogen-doped carbon-coated nano molybdenum carbide has a conductive carbon-coated network structure, and the carbon-coated structure prevents the molybdenum carbide from agglomerating during high-temperature calcination, so that the nitrogen-doped carbon-coated nano molybdenum carbide has excellent electrocatalytic performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention realizes the controllable synthesis of the nitrogen-doped carbon-coated nano molybdenum carbide.
(2) The nitrogen-doped carbon-coated nano molybdenum carbide synthesized by the method has a novel structure, and the hydrogen production performance by electrocatalytic decomposition of water is stable.
(3) The process is simple and controllable, and can be rapidly amplified and industrialized.
Drawings
Fig. 1 is an XRD pattern of nitrogen-doped carbon-coated nano molybdenum carbide prepared in example 1;
FIG. 2 is an XRD pattern of N-doped carbon-coated nano-molybdenum carbide prepared in example 2;
FIG. 3 is an XRD pattern of N-doped carbon-coated nano-molybdenum carbide prepared in example 3;
FIG. 4 is an SEM image of N-doped carbon-coated nano-molybdenum carbide prepared in example 3;
FIG. 5 is a polarization diagram of N-doped carbon-coated nano-molybdenum carbide prepared in example 3;
FIG. 6 is an SEM image of N-doped carbon-coated nano-molybdenum carbide prepared in example 4;
fig. 7 is a polarization curve diagram of the nitrogen-doped carbon-coated nano molybdenum carbide prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
The polarization curve test method described in the examples is as follows:
preparing an electrode: first, a polishing powder (Al) for a Glassy Carbon Electrode (GCE) having a diameter of 3mm was used2O3) Grinding and polishing, and cleaning with ethanol and deionized water for later use. Secondly, weighing 4mg of catalyst into a centrifuge tube, adding 750m L deionized water, 250 μ L of ethanol and 30 μ L of Nafion solution, ultrasonically dispersing uniformly, transferring 5 μ L of the solution to a GCE, and irradiating and drying under an infrared lamp. The calculated catalyst loading was 0.285mg cm-2。
Electrochemical testing: all electrochemical data were measured on CHI 660E electrochemical workstation using a 1.0mol/L KOH solution in N2And (5) purifying. In a typical three-electrode test system, the graphite rod electrode is the counter electrode, the GCE with catalyst is the working electrode, and the Ag/AgCl electrode is the reference electrode. After the catalyst was stabilized in the electrolyte, at 5 mVs-1The polarization curve (LSV) test was performed, all potentials are expressed in Reversible Hydrogen Electrode (RHE), the formula is converted:
ERHE＝EAg/AgCl+0.059pH+Eθ Ag/AgCl
Eθ Ag/AgCl＝0.198V
example 1
The preparation method of the nitrogen-doped carbon-coated nano molybdenum carbide of the embodiment comprises the following specific preparation steps:
dissolving 12.2g of soluble sodium molybdate in deionized water, adding 12.2g of diammonium hydrogen citrate, adding 3.7g of hydrazine hydrochloride after complete dissolution, adjusting the pH value of the solution to 6.0 by using ammonia water, reacting the solution at 40 ℃ for 6 hours, stirring and evaporating at 70 ℃ for 12 hours to obtain gel, and further dehydrating the gel at 120 ℃ for 12 hours to obtain xerogel. The dry gel is evenly ground and put into a tube furnace for carbonization and reduction for 2 hours at 600 ℃, and 5% (v/v) H is introduced during the reaction process2H of (A) to (B)2And (5) carrying out reaction on the/Ar mixed gas to obtain the target product, namely the nitrogen-doped carbon-coated nano molybdenum carbide.
The XRD pattern of the nitrogen-doped carbon-coated nano molybdenum carbide obtained in this example is shown in fig. 1, and the characteristic peaks of XRD of the nitrogen-doped carbon-coated nano molybdenum carbide measured are 36.9 °, 42.8 °, 62.7 ° and 75.3 °, which correspond to the (111), (200), (220) and (311) crystal planes of α -MoC, respectively. The characteristic peak of 24.9 degrees 2 θ corresponds to the (002) crystal face of the graphitized nitrogen-doped carbon. Which indicates that the nitrogen-doped carbon-coated nano molybdenum carbide is successfully synthesized.
Example 2
The preparation method of the nitrogen-doped carbon-coated nano molybdenum carbide of the embodiment comprises the following specific preparation steps:
dissolving 12.2g of soluble ammonium molybdate in deionized water, adding 12.2g of diammonium hydrogen citrate, adding 3.7g of hydrazine hydrochloride after complete dissolution, adjusting the pH value of the solution to 6.5 by using ammonia water, reacting the solution at 40 ℃ for 4 hours, stirring and evaporating at 70 ℃ for 12 hours to obtain gel, and further dehydrating the gel at 140 ℃ for 12 hours to obtain dry gel. Uniformly grinding the xerogel, putting the xerogel into a tubular furnace for carbonization and reduction for 2 hours at 700 ℃, and introducing H containing 5% (v/v) in the reaction process2H of (A) to (B)2And (5) carrying out reaction on the/Ar mixed gas to obtain the target product, namely the nitrogen-doped carbon-coated nano molybdenum carbide.
The XRD pattern of the nitrogen-doped carbon-coated nano molybdenum carbide obtained in this example is shown in fig. 2, and the characteristic peaks of XRD of the nitrogen-doped carbon-coated nano molybdenum carbide measured are 34.3 °, 37.7 °, 39.3 °, 52.1 °, 61.5 °, 69.4 °, 72.4 °, 74.6 ° and 75.5 °, respectively corresponding to β -Mo2The (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of C. The characteristic peak of 24.9 degrees 2 θ corresponds to the (002) crystal face of the graphitized nitrogen-doped carbon. Which indicates that the nitrogen-doped carbon-coated nano molybdenum carbide is successfully synthesized.
Example 3
The preparation method of the nitrogen-doped carbon-coated nano molybdenum carbide of the embodiment comprises the following specific preparation steps:
dissolving 12.2g of soluble ammonium molybdate in deionized water, adding 24.4g of diammonium hydrogen citrate, adding 5.4g of hydrazine hydrochloride after complete dissolution, adjusting the pH value of the solution to 6.5 by using ammonia water, reacting the solution at 40 ℃ for 4 hours, stirring and evaporating at 80 ℃ for 12 hours to obtain gel, and further dehydrating the gel at 160 ℃ for 12 hours to obtain dry gelUniformly grinding the dry gel, putting the dry gel into a tube furnace for carbonization and reduction at 800 ℃ for 4 hours, and introducing H containing 10% (v/v) in the reaction process2H of (A) to (B)2And (5) carrying out reaction on the/Ar mixed gas to obtain the target product, namely the nitrogen-doped carbon-coated nano molybdenum carbide.
The XRD pattern of the nitrogen-doped carbon-coated nano molybdenum carbide obtained in this example is shown in fig. 3, and the characteristic peaks of XRD of the nitrogen-doped carbon-coated nano molybdenum carbide measured are 34.3 °, 37.7 °, 39.3 °, 52.1 °, 61.5 °, 69.4 °, 72.4 °, 74.6 ° and 75.5 °, respectively corresponding to β -Mo2The (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of C. The characteristic peak of 24.9 degrees 2 θ corresponds to the (002) crystal face of the graphitized nitrogen-doped carbon. Which indicates that the nitrogen-doped carbon-coated nano molybdenum carbide is successfully synthesized.
An SEM image of the nitrogen-doped carbon-coated nano molybdenum carbide obtained in this example is shown in fig. 4, wherein the particle size of the nitrogen-doped carbon-coated nano molybdenum carbide is about 4 to 5 nm.
The polarization curve of the N-doped carbon-coated nano-molybdenum carbide obtained in this example is shown in FIG. 5, where the current generated by the N-doped carbon-coated nano-molybdenum carbide is-10 mA cm-2The corresponding bias voltage was-207 mV.
Example 4
The preparation method of the nitrogen-doped carbon-coated nano molybdenum carbide of the embodiment comprises the following specific preparation steps:
dissolving 12.2g of soluble ammonium molybdate in deionized water, adding 36.6g of diammonium hydrogen citrate, adding 4.4g of hydrazine hydrochloride after complete dissolution, adjusting the pH value of the solution to 7.0 by using ammonia water, reacting the solution at 40 ℃ for 4 hours, stirring and evaporating at 80 ℃ for 12 hours to obtain gel, and further dehydrating the gel at 200 ℃ for 12 hours to obtain dry gel. Uniformly grinding the xerogel, putting the xerogel into a tubular furnace for carbonization and reduction at 900 ℃ for 4 hours, and introducing H containing 10% (v/v) in the reaction process2H of (A) to (B)2And (5) carrying out reaction on the/Ar mixed gas to obtain the target product, namely the nitrogen-doped carbon-coated nano molybdenum carbide.
The XRD pattern of the N-doped carbon-coated nano molybdenum carbide obtained in the example is consistent with that of figure 2, and the characteristic peaks of the N-doped carbon-coated nano molybdenum carbide tested by the method are 34.3 degrees, 37.7 degrees and 39.3 degrees52.1 degrees, 61.5 degrees, 69.4 degrees, 72.4 degrees, 74.6 degrees and 75.5 degrees respectively correspond to β -Mo2The (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of C. The characteristic peak of 24.9 degrees 2 θ corresponds to the (002) crystal face of the graphitized nitrogen-doped carbon. Which indicates that the nitrogen-doped carbon-coated nano molybdenum carbide is successfully synthesized.
An SEM image of the nitrogen-doped carbon-coated nano molybdenum carbide obtained in this example is shown in fig. 6, wherein the particle size of the nitrogen-doped carbon-coated nano molybdenum carbide is about 4 to 5 nm.
The polarization curve of the N-doped carbon-coated nano-molybdenum carbide obtained in this example is shown in FIG. 7, where the current generated by the N-doped carbon-coated nano-molybdenum carbide is-10 mA cm-2The corresponding bias voltage was-184 mV.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst is characterized by comprising the following steps of:
(1) preparing a gel: dissolving soluble molybdenum salt in water, adding diammonium hydrogen citrate, adding hydrazine hydrochloride after complete dissolution, uniformly mixing, adjusting the pH value of the solution to 5.5-7 by using ammonia water, heating and reacting for a period of time, continuously heating and stirring until the solution is evaporated to dryness to obtain gel, and further heating and dehydrating the obtained gel to obtain dry gel;
(2) preparing nitrogen-doped carbon-coated nano molybdenum carbide: uniformly grinding the xerogel obtained in the step (1), putting the xerogel into a tubular furnace for high-temperature carbonization and reduction, introducing reducing gas in the reaction process, and obtaining the target product nitrogen-doped carbon-coated nano molybdenum carbide after the reaction is finished;
the heating reaction in the step (1) for a period of time is to heat to 30-50 ℃ for 4-8 h.
2. The method of preparing a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 1, wherein:
the soluble molybdenum salt in the step (1) comprises ammonium molybdate, molybdenum chloride and sodium molybdate.
3. The method of preparing a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 1, wherein:
the dosage of the soluble molybdenum salt, the diammonium hydrogen citrate and the hydrazine hydrochloride in the step (1) meets the following requirements: the mass ratio of diammonium hydrogen citrate to soluble molybdenum salt is (0.5-10) to 1; the mass ratio of the hydrazine hydrochloride to the soluble molybdenum salt is (0.1-2) to 1.
4. The method of claim 3, wherein the nitrogen-doped carbon-coated molybdenum carbide electrocatalyst is prepared by a method comprising:
the dosage of the soluble molybdenum salt, the diammonium hydrogen citrate and the hydrazine hydrochloride in the step (1) meets the following requirements: the mass ratio of diammonium hydrogen citrate to soluble molybdenum salt is (1-3) to 1; the mass ratio of the hydrazine hydrochloride to the soluble molybdenum salt is (0.3-0.44): 1.
5. The method of preparing a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 1, wherein:
heating and stirring in the step (1) until the gel is evaporated to dryness, namely heating to 60-80 ℃ and stirring for 4-24 hours to evaporate to dryness to obtain the gel; the temperature-rising dehydration refers to heating to 100-200 ℃ for reaction for 4-24 h to further dehydrate the gel to obtain xerogel.
6. The method of preparing a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 1, wherein:
the high-temperature carbonization reduction in the step (2) is to react for 2-12 hours at 600-1200 ℃.
7. The method of preparing a nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 1, wherein:
the reducing gas in the step (2) comprises hydrogen and argon/hydrogen mixed gas.
8. A nitrogen-doped carbon-coated molybdenum carbide electrocatalyst prepared according to the method of any one of claims 1 to 7.
9. Use of the nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 8 as an electrocatalytic material.
10. The use of the nitrogen-doped carbon-coated molybdenum carbide electrocatalyst according to claim 8 as an electrocatalytic material for catalytically decomposing water to produce hydrogen gas.
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